EP0257937B1 - Procédé de production d'oxyde d'éthylène - Google Patents

Procédé de production d'oxyde d'éthylène Download PDF

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Publication number
EP0257937B1
EP0257937B1 EP87307198A EP87307198A EP0257937B1 EP 0257937 B1 EP0257937 B1 EP 0257937B1 EP 87307198 A EP87307198 A EP 87307198A EP 87307198 A EP87307198 A EP 87307198A EP 0257937 B1 EP0257937 B1 EP 0257937B1
Authority
EP
European Patent Office
Prior art keywords
catalyst
ethylene oxide
bed
tubes
gases
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP87307198A
Other languages
German (de)
English (en)
Other versions
EP0257937A3 (en
EP0257937A2 (fr
Inventor
Philip Edward Langley
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB868620970A external-priority patent/GB8620970D0/en
Priority claimed from GB868620971A external-priority patent/GB8620971D0/en
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of EP0257937A2 publication Critical patent/EP0257937A2/fr
Publication of EP0257937A3 publication Critical patent/EP0257937A3/en
Application granted granted Critical
Publication of EP0257937B1 publication Critical patent/EP0257937B1/fr
Expired legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
    • C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00823—Mixing elements
    • B01J2208/00831—Stationary elements
    • B01J2208/00849—Stationary elements outside the bed, e.g. baffles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/302—Basic shape of the elements
    • B01J2219/30223—Cylinder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/304—Composition or microstructure of the elements
    • B01J2219/30475—Composition or microstructure of the elements comprising catalytically active material

Definitions

  • THIS INVENTION relates to a process for the production of ethylene oxide.
  • Ethylene oxide is commonly produced by passing ethylene, oxygen and other gases usually including a chlorine containing reaction inhibitor, for example ethylene dichloride or vinyl chloride, through a bed of a suitable catalyst which usually comprises silver on a heat resistant support, for example an ⁇ -alumina support.
  • a suitable catalyst which usually comprises silver on a heat resistant support, for example an ⁇ -alumina support.
  • the catalyst may be packed in the tubes of a tubular reactor, the outside of the tubes being contacted with a heat exchange fluid to control the temperature in the tubes.
  • the gases emerge from the reactor tubes it may be desirable or necessary for mechanical reasons to pass them through a volume of empty or packed space before they are cooled. This may arise for example if the gases are passed from a reactor to a separate cooler, the volume of space in this case comprising any free space in the reactor beyond the reactor tubes, in the pipework and possibly space in the cooler before any cooling tubes. During passage through this space the gases are hot and ethylene oxide tends to isomerise to acetaldehyde, which is difficult to remove from ethylene oxide and may thus contaminate the product.
  • This invention comprises a process of producing ethylene oxide by contacting ethylene and oxygen with a main body of a solid catalyst in a reaction zone, recovering a gaseous reaction product from the said zone and passing it at a temperature at which isomerisation of ethylene oxide to acetaldehyde is significant through a substantial volume to a cooler, characterised in that the acetaldehyde content of the gaseous reaction product is decreased after passage through a substantial part of the said volume by passing it through a second, smaller bed of a catalyst for the oxidation of ethylene with oxygen to ethylene oxide and then cooling it.
  • the main body of catalyst is suitably a fixed bed packed into a tubular reactor.
  • Combustion of ethylene and/or other gases present with the oxygen may occur if the concentration of the oxygen is too high. Whereas this can readily be controlled at the inlet to the reactor tubes and to a lesser extent, by ensuring as far as possible that the tubes are homogeneous when they are first filled with catalyst, at their outlets, we have found that despite operating at oxygen levels which should allow an ample safety factor such combustion can nonetheless occasionally occur at the outlet of the reactor tubes.
  • this difficulty is reduced by rapidly mixing the effluent from the main reactor tubes transversely in the presence of inert packing.
  • the means for transverse mixing may take the form of cooling tubes or cooled baffles, but any means intended to cool the gases during the transverse mixing tends to increase the volume of the mixing zone and thus to delay mixing, and to increase back pressure and we prefer therefore to carry out the mixing without substantial cooling. As acetaldehyde produced by isomerisation during mixing will be consumed in the second bed of catalyst, the lack of cooling is acceptable.
  • Packing elements of this type used in distillation for example the metal or ceramic elements described by W Meyer in the Sulzer Technical Review 2/1979 pages 49 onward may be used. It will be appreciated that the materials used should be temperature and oxygen resistant and should not catalyse undesired side reactions.
  • ethylene oxide may also be formed.
  • the catalyst may be of conventional type, for example it may comprise 3% to 30% and preferably 5 to 20% by weight of silver on a porous heat resisting support, for example an alpha alumina support suitably having a surface area of 0.05 to 10 for example 0.1 to 2 and preferably 0.2 to 1 m2/g and optionally containing an alkali metal for example sodium, potassium, rubidium and/or cesium in a form which may be removed by extraction with water and/or an alkaline earth metal, for example barium.
  • a porous heat resisting support for example an alpha alumina support suitably having a surface area of 0.05 to 10 for example 0.1 to 2 and preferably 0.2 to 1 m2/g and optionally containing an alkali metal for example sodium, potassium, rubidium and/or cesium in a form which may be removed by extraction with water and/or an alkaline earth metal, for example barium.
  • the second bed of catalyst is suitably at least 0.2% preferably 0.5 to 5% and more preferably 0.7 to 3% of the volume of the main body, and may conveniently be similar or identical to that of the main body.
  • the temperatures at which isomerisation of ethylene oxide to acetaldehyde becomes a significant problem are 180 to 300°C.
  • Cooling preferably takes place immediately after passage through the second bed. It may conveniently take place in a conventional heat exchanger.
  • the process of producing ethylene oxide may be conventional, and is normally carried out in the presence of a small quantity of a chlorine containing reaction inhibitor, for example vinyl chloride or ethylene dichloride, for example at a temperature of 200-300°C and a pressure of 0.5 to 30 bars absolute and very suitably is carried out also in the presence of a compound in the gas phase which is capable of forming nitrate and/or nitrite ions in the catalyst as disclosed in out British patent No 2,014,133.
  • a chlorine containing reaction inhibitor for example vinyl chloride or ethylene dichloride
  • the upper part of the reactor 1 comprises externally cooled tubes 2 which are packed with a supported silver catalyst and end in a tube plate 3.
  • a perforated plate 4 supporting packing material sold under the trade name Mellapack by Sulzer.
  • This comprises three layers of corrugated metal sheets 5, 6, and 7 each layer arranged as parallel packs lying at 45° to the vertical, thus connecting rows of reactor tube outlets, each layer being oriented with respect to the one below as rotated about the axis of the reactor through 90° thus connecting the said rows of reactor tube outlets to other rows and thereby mixing effluent from the tubes more thoroughly.
  • the mixed gases pass from reactor 1 through pipe 10 to cooler 11 which comprises tubes 12 through which the gases are passed. They are cooled externally with a heat exchange fluid and end in a tube plate 13 to the under surface of which is held a layer of catalyst 15 identical to that in reactor 1 by means of perforated plate 14 which is bolted to tube plate 13.
  • the cooler is of smaller size than the reactor 1 and consequently access to bed 15 can be readily obtained by disconnecting flanges 16 of the cooler and lifting the upper part of it clear.
  • the reactor bed 15 is about 2.5% of the volume of the bed in reactor 1.
  • a gas stream comprising 30% ethylene, 7.5% oxygen, 6% CO2, 2 ppm vinyl chloride, 0.5 ppm ethyl chloride, the balance being largely methane and inerts with some ethane is passed through the tubes of reactor 1 at an inlet temperature of 140°C and an outlet temperature of 260°C giving an average oxygen conversion of about 40% at a selectivity of ethylene to ethylene oxide of about 75%.
  • any non uniformity of conversion of oxygen in different reactor tubes is compensated by the rapid mixing of the gases from different tubes in packing layers 5, 6 and 7.
  • the gases then pass to cooler 11 in which catalyst bed 15 serves to oxidise at least part of any acetaldehyde formed by isomerisation of ethylene oxide in the space between tubes 2 and bed 15, immediately before the gases are cooled.
  • ppm means parts per million. gas concentrations are by volume.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Epoxy Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (6)

  1. Procédé de production d'oxyde d'éthylène par mise en contact d'éthylène et d'oxygène avec un corps principal de catalyseur solide dans une zone de réaction, récupération d'un produit réactionnel gazeux à partir de cette zone et envoi de celuici à une température à laquelle l'isomérisation de l'oxyde d'éthylène en acétaldéhyde est notable à travers un volume notable vers un refroidisseur, caractérisé en ce que la teneur en acétaldéhyde du produit réactionnel gazeux est réduite après traversée d'une notable partie de ce volume, par envoi du produit à travers un second lit plus petit d'un catalyseur pour l'oxydation de l'éthylène avec de l'oxygène en oxyde d'éthylène et ensuite refroidissement de celui-ci.
  2. Procédé suivant la revendication 1, caractérisé en ce que le corps principal de catalyseur est un lit fixe tassé dans un réacteur tubulaire.
  3. Procédé suivant la revendication 2, caractérisé en ce que les sorties des tubes du réacteur tubulaire débouchent dans une zone dans laquelle des gaz sortant des tubes sont rapidement mélangés transversalement par contact avec des solides.
  4. Procédé suivant la revendication 3, caractérisé en ce que les gaz sont mélangés transversalement sans refroidissement notable.
  5. Procédé suivant la revendication 4, caractérisé en ce que les gaz sont mélangés transversalement au moyen d'éléments de garnissage de matériau métallique ou céramique qui ont une structure ordonnée.
  6. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que le second lit de catalyseur représente 0.5 à 5% du volume du premier lit.
EP87307198A 1986-08-29 1987-08-14 Procédé de production d'oxyde d'éthylène Expired EP0257937B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB8620970 1986-08-29
GB8620971 1986-08-29
GB868620970A GB8620970D0 (en) 1986-08-29 1986-08-29 Ethylene oxide
GB868620971A GB8620971D0 (en) 1986-08-29 1986-08-29 Ethylene oxide

Publications (3)

Publication Number Publication Date
EP0257937A2 EP0257937A2 (fr) 1988-03-02
EP0257937A3 EP0257937A3 (en) 1988-10-12
EP0257937B1 true EP0257937B1 (fr) 1991-03-06

Family

ID=26291230

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87307198A Expired EP0257937B1 (fr) 1986-08-29 1987-08-14 Procédé de production d'oxyde d'éthylène

Country Status (4)

Country Link
US (1) US4847393A (fr)
EP (1) EP0257937B1 (fr)
JP (1) JP2563364B2 (fr)
DE (1) DE3768372D1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2399992A (en) * 1991-08-07 1993-03-02 Olin Corporation Loop reactor for the oxidation of olefins
JP2778878B2 (ja) * 1991-09-12 1998-07-23 株式会社日本触媒 エチレンオキシドの製造方法
US5286884A (en) * 1992-07-24 1994-02-15 Texaco Chemical Company Thermosyphonic reaction of propylene with tertiary butyl hydroperoxide and reactor
US6100412A (en) * 1999-09-10 2000-08-08 Degussa-Huls Ag Process for the epoxidation of olefinic compounds
RU2292946C2 (ru) * 2001-02-08 2007-02-10 Сайентифик Дизайн Компани, Инк. Система для проведения экзотермических реакций
US7294317B2 (en) * 2001-02-08 2007-11-13 Sd Lizenzverwertungsgesellschaft Mbh & Co. Exothermic reaction system
WO2009116977A2 (fr) 2007-12-18 2009-09-24 Dow Technology Investments Llc Réacteur à tube

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1995991A (en) * 1931-04-28 1935-03-26 Du Pont Direct oxidation of olefine hydrocarbons
US3145220A (en) * 1960-11-08 1964-08-18 Exxon Research Engineering Co Method of oxidizing hydrocarbon feeds employing discontinuous triggering means
US3335547A (en) * 1963-07-18 1967-08-15 Halcon International Inc Process for the purification of ethylene oxide
US3483229A (en) * 1965-08-16 1969-12-09 Union Carbide Corp Noncatalytic vapor-phase oxidation of hydrocarbons in a dilution reactor
JPS6045637B2 (ja) * 1978-07-26 1985-10-11 株式会社日本触媒 酸化エチレンの製造方法

Also Published As

Publication number Publication date
JP2563364B2 (ja) 1996-12-11
EP0257937A3 (en) 1988-10-12
DE3768372D1 (de) 1991-04-11
US4847393A (en) 1989-07-11
JPS63190881A (ja) 1988-08-08
EP0257937A2 (fr) 1988-03-02

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